CN106807936A - A kind of processing method of the gold nano grain of organo-functional group protection - Google Patents
A kind of processing method of the gold nano grain of organo-functional group protection Download PDFInfo
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- CN106807936A CN106807936A CN201510869348.9A CN201510869348A CN106807936A CN 106807936 A CN106807936 A CN 106807936A CN 201510869348 A CN201510869348 A CN 201510869348A CN 106807936 A CN106807936 A CN 106807936A
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- lewis acid
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Abstract
A kind of processing method of the gold nano grain of organo-functional group protection, the method can simply and efficiently process gold nano grain surface stabilizer part, to provide unsaturated coordination atom, improve its catalysis activity.The method is mainly by adding Lewis acid in gold nano grain, under the synergy of alkali, there is provided lone electron pair, the stabilizer part of gold surface can be processed at room temperature.Can be visually observed that very much in UV-visible absorption spectrum Lewis acid add after absworption peak change, these change and mass spectrogram on result be also identical.
Description
Technical field
The invention belongs to technical field of nano material, one kind of more particularly to gold nano grain surface organic ligands removal is new
Method.
Background technology
In recent years, the characteristic such as noble metal nanometer material unique light, electricity, catalysis and its study in new energy, light
The application in the fields such as power information storage, biologic medical is subject to the extensive concern of Related Research Domain.Noble metal nano
The widely used chemical method based on liquid phase of particle preparation method：With body before certain template compound and noble metal
Body is reduced by specific reducing agent, under the stabilization and protection of template compound so that precious metal ion
Gradually it is reduced to noble metal nano particles.In building-up process, these stabilizer parts are preventing noble metal former
Critically important effect served and irreversible reunion aspect in the interphase interaction of son there is.Once but noble metal nano grain
Son is deposited on substrate, and the metallic of these coordination saturations is because the presence of part seriously reduces its catalysis activity
Deng some application aspects.
So far, the method for the treatment of gold nano grain surface organic ligands still there are problems that.Pass through
While the mode of heating and oxidation processes part, can also change the size and pattern of particle, further influence it
Catalysis activity.Hutchings seminars propose with solvent-extracted method to remove Au-PVA's within 2011
Part PVA.However, this kind of method is not particularly suited for excision as covalent bond strong between Au-S.This patent pin
To this problem, invent with the method for Lewis acid treatment gold nano grain surface organic ligands.
The content of the invention
It is an object of the invention to provide a new method for treatment gold nano grain surface organic ligands.The method is operated
Simply, the size of golden nanometer particle is not destroyed, can significantly improve its catalysis activity.
The present invention seeks to what is be accomplished by the following way：
With Au25(SR)18As a example by (SR is thiol ligand), its part, specific bag are removed by adding Lewis acid
Include following experimental procedure：With HAuCl4·4H2O is reaction raw materials, and three mouthfuls of round bottoms for being placed on 50ml burn
In bottle, it is dissolved in a certain amount of tetrahydrofuran (THF) system, adds ammonium bromide and tetraoctyl ammonium bromide (TOAB),
Stirring certain hour, adds appropriate benzene ethyl mercaptan (PhCH2CH2SH), after solution is water white transparency,
It is disposable to add reducing agent sodium borohydride (NaBH4), reaction can obtain for three hours, be washed with methyl alcohol and n-hexane,
Removal insoluble matter is dissolved with dichloromethane (DCM), volatilize dichloromethane, the Au for obtaining25(SR)18With not
Same Lewis acid treatments, by ultraviolet-uisible spectrophotometer (UV) and matrix assisted laser desorption ionization electricity
Compare experiment to observe it to Au from mass-spectrometric technique (MADLI-MS)25(SR)18Effect.
1. processing method described in, it is characterised in that：Gold nano grain is soaked in Lewis acid solutions.
2. processing method described in, it is characterised in that：Lewis acid is NiCl2, Co (OAc)2, Cu (OAc)2,
Cu(OAc)1, or Cr (NO3)3The solvent that molar concentration 0.028-0.14mmol/L, Lewis acid solution are used
It is water, ethanol or methyl alcohol.
3. processing method described in, it is characterised in that：Soak time is 1-10h or so, with Lewis acid treatments
Effect is different and slightly distinguish.
4. processing method described in, it is characterised in that：Control Lewis acid and Au25(SR)18Mol ratio be 2：
1-5。
5. processing method described in, it is characterised in that：Control immersion reaction is carried out at 20-30 DEG C of normal temperature.
6. processing method described in, it is characterised in that：Organic base collaboration is also needed to while adding Lewis acid to make
With, organic base is also added in Lewis acid solutions, organic base is ammoniacal liquor or pyridine, and whole mole of organic base is dense
Degree 0.05-0.3mol/L.
Beneficial effect of the present invention is：
(1) the treatment gold nano grain method that the present invention is studied is applicable not only to weak interaction force, more applicable
In these strong Au-S covalent bonds.
(2) the treatment gold nano grain method that the present invention is studied need not be heated or aoxidized to nano particle,
Do not destroy its structure and size significantly.
(3) the optional scope of Lewis acid is wide used in the treatment gold nano grain method that the present invention is studied, operation
Step is simple.
(4) after the treatment gold nano grain that the present invention is studied, catalysis activity is obviously improved.
Brief description of the drawings
Fig. 1 is Au prepared by embodiment 125(SR)18Transmission electron microscope figure (TEM).
Fig. 2 is Au in embodiment 2 and embodiment 325(SR)18Sample is with Co (OAc)2Mass spectrogram after before processing.
Fig. 3 is addition Co (OAc) in embodiment 42With the Au of pyridine25(SR)18Electrospray ionization mass spectrum figure.
Fig. 4 is only addition Co (OAc) in embodiment 52Au25(SR)18Stir different time sections when it is ultraviolet-can
See abosrption spectrogram (UV-Vis).
Fig. 5 is addition Co (OAc) in embodiment 62And NH3·H2The Au of O25(SR)18In stirring different time sections
When UV-visible absorption spectrum (UV-Vis).
Fig. 6 be embodiment 7 in add NiCl2And NH3·H2The Au of O25(SR)18When different time sections are stirred
UV-visible absorption spectrum (UV-Vis).
Fig. 7 is addition Cu (OAc) in embodiment 82And NH3·H2The Au of O25(SR)18In stirring different time sections
When UV-visible absorption spectrum (UV-Vis).
Fig. 8 is in the embodiment 9 50 DEG C Au of addition ammoniacal liquor25(SR)18Ultraviolet when different time sections are stirred-can
See abosrption spectrogram (UV-Vis).
Specific embodiment
Below in conjunction with the accompanying drawings and specific implementation case come the present invention is described in further detail.
Embodiment 1：Au25(SR)18Synthesis
Weigh the HAuCl of 60mg4·4H2O is added in 50mL there-necked flasks, adds 15mL THF, solution
It is golden yellow.Add TOAB 92mg (TOAB：Au=1.16mol：1mol), solution is by golden yellow slow
It is slow to deepen to be orange red.After stirring 30min, PhCH is added2CH2SH 97μL(PhCH2CH2SH：Au=5
mol：1mol), solution colour gradually become shallower as to it is colourless when, add NaBH4(4mL frozen water) 55mg
(NaBH4：Au=10mol：1mol).Stirring three hours, stops reaction.Product is washed with n-hexane and methyl alcohol
Thing, precipitation dichloromethane is dissolved, and removes insoluble matter, and Au is obtained after drying25(SR)18。
If Fig. 1 is gold nanoclusters transmission electron microscope picture prepared by embodiment 1, a diameter of 1.5nm of gold grain
Left and right.
Embodiment 2：Au25(SR)18Middle addition ammoniacal liquor
Under room temperature condition, common 1mL dissolves 1mg's during dichloromethane and methyl alcohol are added into sample bottle in equal volume
Au25(SR)18, add the ammoniacal liquor (NH of 5 μ L3·H2O, mass percentage concentration is 25%), to be processed
Preceding sample.
As spectrogram is the Au of an addition ammoniacal liquor in embodiment 2 below in Fig. 225(SR)18Mass spectrogram.Can by figure
To find out that it correspond to Au25(SR)18Karyoplasmic ratio (m/z:7394.3) with its fragment karyoplasmic ratio (m/z:6058.1).
Embodiment 3：Sample is with Co (OAc)2Treatment
The Au of 1mg will be dissolved in dichloromethane and methyl alcohol in equal volume common 1mL additions sample bottle25(SR)18, plus
Enter the ammoniacal liquor (NH of 5 μ L3·H2O, mass percentage concentration is 25%), to add 0.14 μm of Co of ol (OAc)2
(Co2+：Au25(SR)18=2:1) 10h, is stirred at room temperature.
As in Fig. 2 above spectrogram be in embodiment 3 sample with Co (OAc)2Mass spectrogram after treatment.Can by figure
Find out that it correspond to Au24(SR)17Karyoplasmic ratio be 7060.3.Do not occur in figure below this peak, it was demonstrated that
Au24(SR)17It is not occur in mass spectrometric measurement, but Co (OAc)2Result.
Embodiment 4：It is pyridine to change the alkali in embodiment 3：Au25(SR)18Middle addition Co (OAc)2And pyridine
The Au of 1mg will be dissolved in dichloromethane and methyl alcohol in equal volume common 1mL additions sample bottle25(SR)18, plus
Enter 5 μ L pyridines, add 0.14 μm of Co of ol (OAc)2(Co2+：Au25(SR)18=2:1), room temperature is stirred
Mix 10h.
If Fig. 3 is addition Co (OAc) in embodiment 42With the Au of pyridine25(SR)18Electrospray ionization mass spectrum figure.From figure
In it can be seen that ion I-VI and VII-IX be respectively 1+and 2+ ions.Each peak corresponds to as follows respectively:
Peak I (m/z=7997.87)-[Au25(SC2H4Ph)18Co4Py3Cs]+
II(7663.87)-[Au25(SC2H4Ph)18CoPyCs]+；Peak III
(7328.91)-[Au24(SC2H4Ph)17CoPyCs]+；Peak IV
(6994.94)-[Au23(SC2H4Ph)16CoPyCs]+；Peak V (6660.93)-[Au22(SC2H4Ph)15CoPyCs]+；
Peak VI (6326.86)-[Au21(SC2H4Ph)14CoPyCs]+；Peak VII
(4065.40)-[Au25(SC2H4Ph)18Co4Py3Cs2]2+；Peak VIII
(3898.40)-[Au25(SC2H4Ph)18CoPyCs2]2+；Peak IX
(3731.42)-[Au24(SC2H4Ph)17CoPyCs2]2+。
Embodiment 5：Au25(SR)18In only add Co (OAc)2
The Au of 1mg will be dissolved in dichloromethane and methyl alcohol in equal volume common 1mL additions sample bottle25(SR)18, plus
Enter 0.14 μm of Co of ol (OAc)2(Co2+：Au25(SR)18=2:1), stir at room temperature.
If Fig. 4 is only addition Co (OAc) in embodiment 52Au25(SR)18When different time sections are stirred
UV-visible absorption spectrum (UV-Vis).As seen from the figure, with the lengthening of mixing time, 670nm
Characteristic peak peak intensity gradually weakens, and shows nano-cluster Au25(SR)18It is slowly converted to other nano-clusters
(Au25-n(SR)18-n, n=1-4).
Embodiment 6：Ammoniacal liquor is added in embodiment 5
The Au of 1mg will be dissolved in dichloromethane and methyl alcohol in equal volume common 1mL additions sample bottle25(SR)18, plus
Enter the ammoniacal liquor (NH of 5 μ L3·H2O, mass percentage concentration is 25%), to add 0.14 μm of Co of ol (OAc)2
(Co2+：Au25(SR)18=2:1), stir at room temperature.
If Fig. 5 is addition Co (OAc) in embodiment 62And NH3·H2The Au of O25(SR)18It is different in stirring
UV-visible absorption spectrum (UV-Vis) during the time period.As seen from the figure, in the synergy of alkali
Under, faster, spectrogram has turned into a decay curve to the speed that 670nm characteristic peaks peak intensity weakens after 60min.
Embodiment 7：The Lewis acid changed in embodiment 6 is NiCl2
The Au of 1mg will be dissolved in dichloromethane and methyl alcohol in equal volume common 1mL additions sample bottle25(SR)18, plus
Enter the ammoniacal liquor (NH of 5 μ L3·H2O, mass percentage concentration is 25%), to add 0.14 μm of NiCl of ol2
(Ni2+：Au25(SR)18=2:1), stir at room temperature.
As Fig. 6 be embodiment 7 in add NiCl2And NH3·H2The Au of O25(SR)18In stirring different time
UV-visible absorption spectrum (UV-Vis) during section.Ni as seen from the figure2+And Co2+There is effect same,
What simply peak intensity weakened slows.
Embodiment 8：The Lewis acid changed in embodiment 6 is Cu (OAc)2
The Au of 1mg will be dissolved in dichloromethane and methyl alcohol in equal volume common 1mL additions sample bottle25(SR)18, plus
Enter the ammoniacal liquor (NH of 5 μ L3·H2O, mass percentage concentration is 25%), to add 0.14 μm of Cu of ol (OAc)2
(Cu2+：Au25(SR)18=2:1), stir at room temperature.
If Fig. 7 is addition Cu (OAc) in embodiment 82And NH3·H2The Au of O25(SR)18It is different in stirring
UV-visible absorption spectrum (UV-Vis) during the time period.Cu as seen from the figure2+And Ni2+Have same
Effect, what simply peak intensity weakened slows.
Embodiment 9：Temperature is 50 DEG C in changing embodiment 2
Dichloromethane and methyl alcohol are added the Au of common 1mL dissolvings 1mg in sample bottle in equal volume25(SR)18, then
Add the ammoniacal liquor (NH of 5 μ L3·H225%) O, mass percentage concentration is in stirring at 50 DEG C.
If Fig. 8 is in the embodiment 9 50 DEG C Au of addition ammoniacal liquor25(SR)18It is purple during stirring different time sections
Outward-visible absorption spectra figure (UV-Vis).It can be seen that alkali is intended only as promoting in processing procedure
Enter agent.
Claims (7)
1. the processing method of the gold nano grain of a kind of organo-functional group protection, gold nano grain is for gold nano grain
The nanocluster protected by organic ligand, it is characterised in that：Gold nano grain is soaked in Lewis acid solutions.
2. processing method according to claim 1, it is characterised in that：Lewis acid is Co (OAc)2、NiCl2、
Cu(OAc)2、Cu(OAc)1Or Cr (NO3)3In one or two or more kinds, molar concentration 0.028-0.14
The solvent that mmol/L, Lewis acid solution are used is one or two or more kinds in water, ethanol or methyl alcohol.
3. processing method according to claim 1, it is characterised in that：Soak time is 1-10h or so, with
Lewis acid treatments effect difference and slightly distinguish.
4. processing method according to claim 1, it is characterised in that：Control Lewis acid and nanocluster
Mol ratio is 2：1-5.
5. processing method according to claim 1, it is characterised in that：Control immersion reaction is in 20-30 DEG C of normal temperature
Under carry out.
6. processing method according to claim 1, it is characterised in that：Also needed to while adding Lewis acid
Organic base is acted synergistically, and organic base is also added with Lewis acid solutions, and organic base is ammoniacal liquor or pyridine, is had
The whole molar concentration 0.05-0.3mol/L of machine alkali.
7. processing method according to claim 1, it is characterised in that：The nanocluster protected by organic ligand
It is Au-PVP, Au-C2H、Aun(SR)m(SR can be SC2H4Ph, 2- naphthyl mercaptan or Buddha's warrior attendant alkanethiol etc.
In one or two or more kinds, n=25, m=18；N=144, m=60；One kind in n=38, m=24 etc. or
More than two kinds) or Au11 (PPh3)7Cl3In one or two or more kinds.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112237945A (en) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination |
| CN114106345A (en) * | 2021-10-19 | 2022-03-01 | 西北工业大学宁波研究院 | Luminous copper-thiol polymer single crystal and preparation method thereof |
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| JP5750833B2 (en) * | 2009-04-10 | 2015-07-22 | 住友化学株式会社 | Metal composite and composition thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112237945A (en) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination |
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| CN114106345A (en) * | 2021-10-19 | 2022-03-01 | 西北工业大学宁波研究院 | Luminous copper-thiol polymer single crystal and preparation method thereof |
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Application publication date: 20170609 |